The structure and thermochemistry of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1) and some related compounds

Condensed and gas phase enthalpies of formation of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1, (−199.1 ± 16.4), (−70.5 ± 20.5) kJ mol⁻¹, respectively) and 3,4,6,7-dibenzobicyclo[3.2.1]nona-3,6-dien-2-one (2, (−79.7 ± 22.9), (20.1 ± 23.1) kJ mol⁻¹) are reported. Sublimation enthalpies at T=298.15 K for these compounds were evaluated by combining the fusion enthalpies at T = 298.15 K (1, (12.5 ± 1.8); 2, (5.3 ± 1.7) kJ mol⁻¹) adjusted from DSC measurements at the melting temperature (1, (T _fus, 357.7 K, 16.9 ± 1.3 kJ mol⁻¹)); 2, (T _fus, 383.3 K, 10.9 ± 0.1) kJ mol⁻¹) with the vaporization enthalpies at T = 298.15 K (1, (116.1 ± 12.1); 2, (94.5 ± 2.2) kJ mol⁻¹) measured by correlation-gas chromatography. The vaporization enthalpies of benzoin ((98.5 ± 12.5) kJ mol⁻¹) and 7-heptadecanone ((94.5 ± 1.8) kJ mol⁻¹) at T = 298.15 K and the fusion enthalpy of phenyl salicylate (T _fus, 312.7 K, 18.4 ± 0.5) kJ mol⁻¹) were also determined for the correlations. The crystal structure of 1 was determined by X-ray crystallography. Compound 1 exists entirely in the enol form and resembles the crystal structure found for benzoylacetone.     

Thermochemical parameters of dimethyl and di-iso-propyl dithiocarbamate complexes of palladium(II)

The standard molar enthalpy of formation of crystalline dialkyldithiocarbamate chelates, [Pd(S₂CNR₂)₂], with R=CH₃ and i-C₃H₇, was determined through reaction-solution calorimetry in 1,2-dichloroethane, at 298 K. Using the standard molar enthalpies of formation of the gaseous chelates, the homolytic (526±18 and 666±10) and heterolytic (2693±18 and 2957±10 kJ mol^-1) mean enthalpies of palladium-sulphur bond dissociation were calculated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermochemical study of 2- and 3-alkyl substituted thiophenes

The standard (p ⁰=0.1 MPa) molar enthalpies of formation, in the condensed phase, of nine linear-alkyl substituted thiophenes, six in position 2- and three in position 3-, at T=298.15 K, were derived from the standard massic energies of combustion, in oxygen, to yield CO₂(g) and H₂SO₄·115H₂O(aq), measured by rotating-bomb combustion calorimetry. The standard molar enthalpies of vaporization of these compounds were measured by high temperature Calvet Microcalorimetry, so their standard molar enthalpies of formation, in the gaseous phase, were derived. The results are discussed in terms of structural contributions to the energetics of the alkyl-substituted thiophenes, and empirical correlations are suggested for the estimation of the standard molar enthalpies of formation, at T=298.15 K, for 2- and 3-alkyl-substituted thiophenes, both in the condensed and in the gaseous phases.     

Thermodynamics of vaporization of gallium trichloride

The unsaturated and saturated pressures of gallium trichloride vapor were measured by the static method with membrane-gauge manometers in wide pressure (0.2–760 Torr) and temperature (313–1071 K) intervals. Scanning calorimetry was used to determine the thermodynamic characteristics of GaCl₃ fusion. The thermodynamic characteristics were obtained for sublimation, fusion, vaporization, and association in the vapor of GaCl₃ molecules. The enthalpies of formation and the absolute entropies of GaCl₃ in the liquid and gaseous phases and Ga₂Cl₆ in the gaseous phase were calculated using literature data. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1266–1269, July, 2007.     

Thermodynamic characteristics of thermal dissociation of platinum dichloride

The dissociation pressure for the process PtCl₂(s) → Pt(s) + Cl₂(g) was measured by the static method with diaphragm zero-pressure gauges. The approximating equation for the temperature dependence on the dissociation pressure for the above reaction was found. The enthalpy (137.7±0.3 kJ mol⁻¹) and entropy (163.6±0.4 J mol⁻¹ K⁻¹) of PtCl₂(s) dissociation and enthalpies of formation and absolute entropies of platinum di- and trichlorides at 298.15 K were calculated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1345–1348, June, 2005.     

An examination of the vaporization enthalpies and vapor pressures of pyrazine, pyrimidine, pyridazine, and 1,3,5-triazine

The vaporization enthalpies and liquid vapor pressures from T = 298.15 K to T = 400 K of 1,3,5-triazine, pyrazine, pyrimidine, and pyridazine using pyridines and pyrazines as standards have been measured by correlation-gas chromatography. The vaporization enthalpies of 1,3,5-triazine (38.8 ± 1.9 kJ mol⁻¹) and pyrazine (40.5 ± 1.7 kJ mol⁻¹) obtained by these correlations are in good agreement with current literature values. The value obtained for pyrimidine (41.0 ± 1.9 kJ mol⁻¹) can be compared with a literature value of 50.0 kJ mol⁻¹. Combined with the condensed phase enthalpy of formation in the literature, this results in a gas-phase enthalpy of formation, Δ_f H _m (g, 298.15 K), of 187.6 ± 2.2 kJ mol⁻¹ for pyrimidine, compared to a value of 195.1 ± 2.1 calculated for pyrazine. Vapor pressures also obtained by correlation are used to predict boiling temperatures (BT). Good agreement with experimental BT (±4.2 K) including results for pyrimidine is observed for most compounds with the exception of the pyridazines. The results suggest that compounds containing one or two nitrogen atoms in the ring are suitable standards for correlating various heterocyclic compounds provided the nitrogen atoms are isolated from each other by carbon. Pyridazines do not appear to be evaluated correctly using pyridines and pyrazines as standards.     

A versatile and high-precision solution—reaction isoperibol calorimeter

A new solution-reaction isoperibol calorimeter was developed to measure enthalpies of solution and reaction. A new system of sample cell was developed to avoid the breaking of glass ampoules, hence making the sample cell reusable. The system is suitable for measuring molar enthalpies of solid-liquid and liquid-liquid interactions at different temperatures. The reproducibility and accuracy of the apparatus were tested by measuring the enthalpy of solution of KCl in water at 298.15 K and the enthalpy of protonation of THAM in HCl (0.1 M) at 298.15 K. The results showed the uncertainty taken as the reproducibility was ±0.3% and the difference with the literature values was within ±0.5%.     

The sublimation enthalpy of dimethyl oxalate

The sublimation enthalpy of dimethyl oxalate has been measured by calorimetric and head space analysis. These results along with vaporization enthalpy measured by correlation gas chromatography and fusion enthalpy measurements are compared to results predicted by two estimation techniques. A previous experimental measurement was found to be in error. A mean value of (75.2±0.5) kJ/mol was obtained which results in a corrected molar value of (–681.5±0.8) kJ/mol for the enthalpy of formation of gaseous dimethyl oxalate, _f H _m ^o (g, 298.15 K). This new value of _f H _m ^o (g, 298.15 K) for dimethyl oxalate, in combination with other enthalpies of formation, suggests that the ground state of oxalates are destabilized relative to -diketones by approximately 25 kJ/mol.     

Determination of the Enthalpies of Formation of DyI2 and DyI3 and estimation of the Dy3+/Dy2+ standard aqueous electrode potential

DyI₂ and Dy_3I were synthesized by literature techniques. Their enthalpies of solution were determined and their enthalpies of formation calculated to be Δ_fH°(DyI₂, s, 298 K) = ?(394 ± 16) kJ· mol^?1 and Δ_fH°(DyI₃, s, 298 K) = ?(616 ± 10) kJ· mol^?1. With appropriate literature and estimated enthalpies of solution and standard entropies, the E°(Dy³⁺/Dy²⁺, aq) was calculated to be ?(2.6 ± 0.2) V. A comparison is made of the enthalpies of reduction of DyI₃ to DyI₂ and of DyCl₃ to DyCl₂.     

Aprotic Ionic Liquids: A Framework for Predicting Vaporization Thermodynamics

Ionic liquids (ILs) are recognized as an environmentally friendly alternative to replacing volatile molecular solvents. Knowledge of vaporization thermodynamics is crucial for practical applications. The vaporization thermodynamics of five ionic liquids containing a pyridinium cation and the [NTf₂] anion were studied using a quartz crystal microbalance. Vapor pressure-temperature dependences were used to derive the enthalpies of vaporization of these ionic liquids. Vaporization enthalpies of the pyridinium-based ionic liquids available in the literature were collected and uniformly adjusted to the reference temperature T = 298.15 K. The consistent sets of evaluated vaporization enthalpies were used to develop the “centerpiece”-based group-additivity method for predicting enthalpies of vaporization of ionic compounds. The general transferability of the contributions to the enthalpy of vaporization from the molecular liquids to the ionic liquids was established. A small, but not negligible correction term was supposed to reconcile the estimated results with the experiment. The corrected “centerpiece” approach was recommended to predict the vaporization enthalpies of ILs.     

Thermodynamic properties of spinel MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: A mass spectrometric study

The activities of oxides in stoichiometric spinel MgAl₂O₄ in the temperature range 1851–2298 K were determined from the data obtained by the Knudsen effusion mass spectrometry. The resulting Gibbs energies of spinel formation from simple oxides, the enthalpies and entropies of spinel formation from simple oxides (–12.02 ± 1.14 kJ/mol and 5.03 ± 0.56 J/(mol K), respectively), and the spinel melting enthalpy (55.81 ± 4.62 kJ/mol) satisfactorily agree with the available thermodynamic data.     

Thermodynamic study of the vaporization of uracil

The vapour pressure of uracil was measured in the temperature range 452–587 K using different techniques and the pressure—temperature equation log P(kPa) = 12.13 ± 0.50 — (6823 ± 210)/T was derived. The thermodynamic functions of gaseous and solid uracil were also evaluated through spectroscopic and calorimetric measurements. The sublimation enthalpy of uracil, ΔH⁰₂₉₈ = 131 ± 5 kJ mole^?1, was derived from second and third law treatment of the vapour data.     

Some thermodynamic properties of benzocaine

The vaporization enthalpy of benzocaine, ethyl 4-aminobenzoate, has been evaluated using correlation gas chromatography at 298.15 K. The temperature dependence of retention time has also been used to evaluate the vapor pressure of the sub-cooled liquid from 298.15 K to the fusion temperature, 365.2 K, by correlation with the vapor pressures of the compounds used as standards. The vaporization enthalpy calculated from the vapor pressures of benzocaine at the melting point was combined with the experimental fusion enthalpy to evaluate the sublimation enthalpy at the fusion temperature. Application of the Clausius–Clapeyron equation together with the vapor pressure common to both phases permitted calculation of the vapor pressure of the solid at 298.15 K. Similar calculations were performed for two of the standards that were solids for comparisons with experimental data. Vaporization and sublimation enthalpies of (91.8 ± 4.2) and (112.9 ± 4.3) kJ mol^?1 are calculated for benzocaine at 298.15 K as are vapor pressures of 0.0083 and 0.0018 Pa for the sub-cooled liquid and crystalline material, respectively.     

Uber die Thermodynamik der Verdampfung von Scandium(III)-fluorid

On the thermodynamics of vapourization of scandium(III) fluoride The vapourization behaviour of solid ScF₃ was studied by the KNUDSEN effusion method. ScF₃ vapourizes congruently with practically stoichiometric composition in a high vacuum at temperatures from 1300 to 1600°K. Within the temperature ranges 1336–1400K and 1440–1528°K the vapourization was found to obey the equations respectively, assuming monomeric ScF3 to be the predominant gaseous species. By considering literature data for the vapourisation behaviour of AlF₃(s) and LaF3(s) the content of SC₂F₆ (g) in the saturated vapour over SeF₃ (s) was estimated to be approximately 0.3% at 1368 ° K. Second an Third Law calculations were performed using known and estimated thermodynamic data for ScF₃(g) and ScF₃(s), respectively, and the enthalpies and the enthalpies and entropies of vapourization at 298.15 ° K were obtained (data see “Inhaltsübersicht”). A. critical discussion of the experimental and theoretical results allowed to conclude that vapour pressures of ScF₃(s), which were determined by others within were found to be three to four orders of magnitude higher than the vapour pressures determined in this work where are are less probable.     

Thermochemical properties of three piperidine derivatives

The standard (p ^o=0.1 MPa) molar energies of combustion for the crystalline 1-benzyl-4-piperidinol and 4-piperidine-piperidine, and for the liquid 4-benzylpiperidine, were measured by static bomb calorimetry, in oxygen, at T=298.15 K. The standard molar enthalpies of sublimation or vaporization, at T=298.15 K, of these three compounds were determined by Calvet microcalorimetry. Those values were used to derive the standard molar enthalpies of formation, at T=298.15 K, in their condensed and gaseous phase, respectively.     

Thermodynamic functions of lactones in the gaseous state

The temperature dependences of the vapor pressures of oxacyclobutan-2-one and oxacyclopentan-2-one were measured by the transpiration method. The entropies of gaseous oxacycloalkan-2-ones (lactones) were determined based on the experimental values of entropy in the condensed state, vapor pressure, and enthalpy of vaporization. Thermodynamic functions of lactones with a ring size of n = 4—8 (number of atoms in the ring) were determined by quantum chemistry and statistical physics methods in the ideal gas approximation taking into account the molar fractions of all conformers and optical isomers in the temperature range from 298.15 to 1500 K. The enthalpies of ring strain were calculated based on the enthalpies of formation.     

Thermochemische Untersuchungen zu den Systemen Ti/Ni und Ti/Co

Thermochemical Investigations of the Systems Ti/Ni and Ti/Co By treatment of solid Ni or Co with a H₂/TiCl₄-gas mixture at sufficient high temperature (T ≥ 900°C) the intermetallic phases TiNi₃ and TiCo₃, resp., are formed. The conversion grade depends on the H₂/TiCl₄-ratio. From the experimentally determined conversion grades and the known thermodynamic data of all other species existing in equilibrium the free enthalpies and the heats of formation of TiN₃ and TiCo₃ have been calculated (TiNi₃: ΔH(298) = ?133.3 ± 6 kJ/mol; TiCo₃: ΔH(298) = ?104.7 ± 6 kJ/mol).     

Standard enthalpy of formation of platinum hydrous oxide

Standard enthalpies of formation of amorphous platinum hydrous oxide PtH_2.76O_3.89 (Adams' catalyst) and dehydrated oxide PtO_2.52 at T=298.15 K were determined to be -519.6±1.0 and -101.3 ±5.2 kJ mol^-1, respectively, by micro-combustion calorimetry. Standard enthalpy of formation of anhydrous PtO₂ was estimated to be -80 kJ mol^-1 based on the calorimetry. A meaningful linear relationship was found between the pseudo-atomization enthalpies of platinum oxides and the coordination number of oxygen surrounding platinum. This relationship indicates that the Pt-O bond dissociation energy is 246 kJ mol^-1 at T=298.15 K which is surprisingly independent of both the coordination number and the valence of platinum atom. This may provide an energetic reason why platinum hydrous oxide is non-stoichiometric. This revised version was published online in August 2006 with corrections to the Cover Date.     

Experimental Enthalpies of Formation and Strain of the Methylated 1-Amino-2-phenylethanes

The standard molar enthalpies of formation H _f ^00B0; (liq) at the temperature t = 298.15 K were determined using combustion calorimetry for N-methyl-3-methyl-3-phenyl-2-butaneamine 1a, N,N-dimethyl-3-methyl-3-phenyl-2-butaneamine 1b N-methyl-2,3-dimethyl-3-phenyl-2-butaneamine 2a, and N,N-dimethyl-2,3-dimethyl-3-phenyl-2-butaneamine 2b. The standard molar enthalpies of vaporization H _vap ^00B0; of these compounds were obtained from the temperature variation of the vapor pressure measured in a flow system. The following standard molar enthalpies of formation in gaseous phase H _f ^00B0; (g) are obtained from these data: for 1a – 10.9 ± 1.9; 1b – 3.6 ± 1.8; 1c – 26.6 ± 1.4, and 1d – 23.0 ± 1.8 kJ mol^–1. From the standard molar enthalpies of formation for gaseous compounds which are available in the literature, improved values for the increments of the Benson group addivitiy scheme of amines were calculated. They are used to determine the strain enthalpies of the amines 1 and 2 from this investigation.     

Physikalische und spektroskopische daten von trifluormethylselenol und derivaten

The characterization of the compounds CF₃SeX (X = H, Cl, Br, CN, CF₃, SeCF₃) is completed by the report of melting points, boiling points, enthalpies of vaporization and entropies of vaporization. Ultraviolet and mass spectra are presented and discussed. An improved synthesis for CF₃SeH is reported.